Structures and chemical bonding of boron-based B12O and B11Au clusters. A counterexample in boronyl chemistry,Physical Chemistry Chemical Physics

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Structures and chemical bonding of boron-based B12O and B11Au clusters. A counterexample in boronyl chemistry
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-04-25 , DOI: 10.1039/d2cp01277d
Peng-Fei Li ₁ , Hua-Jin Zhai ₁

Affiliation

Boron oxide clusters have structural diversity and unique chemical bonding, and recent literature has shown that boronyl complexes dominate boron-rich oxide clusters. A counterexample in boronyl chemistry is presented in this work. Using global structural searches, electronic structure calculations, and chemical bonding analyses, we shall report on the computational design of two boron-based quasi-planar or planar clusters: B₁₂O and B₁₁Au. Contrary to expectation, the B₁₂O cluster has a circular quasi-planar shape with a peripheral B–O–B bridge, which resembles bare B₁₂ cluster. It does not contain a boronyl ligand. The isomeric boronyl complex turns out to be 10.32 kcal mol⁻¹ higher in energy at the single-point CCSD(T) level. In contrast, B₁₁Au cluster behaves normally with an elongated B₁₁ moiety and a terminal Au ligand. Chemical bonding analyses reveal three-fold π/σ aromaticity in circular B₁₂O cluster, including global 6π aromaticity, as well as spatially isolated inner 2σ aromaticity and outer 10σ aromaticity. The three-fold 6π/2σ/10σ aromaticity underlies the stability of B₁₂O cluster. This bonding picture is unknown for bare B₁₂ cluster and its derivatives. The elongated B₁₁Au cluster has conflicting π/σ aromaticity (with 6π versus 8σ electron-counting). The B₁₂O cluster is actually isoelectronic with bare B₁₂ cluster in terms of delocalized π/σ bonding, which inherits the structural and electronic robustness of the latter.

中文翻译：

硼基 B12O 和 B11Au 簇的结构和化学键合。硼基化学的反例

氧化硼簇具有结构多样性和独特的化学键，最近的文献表明硼基配合物在富硼氧化物簇中占主导地位。在这项工作中提出了硼基化学的一个反例。使用全局结构搜索、电子结构计算和化学键分析，我们将报告两个基于硼的准平面或平面簇：B ₁₂ O 和 B ₁₁ Au 的计算设计。与预期相反，B ₁₂ O 星团具有圆形准平面形状，外围有一个 B-O-B 桥，类似于裸 B ₁₂星团。它不含硼基配体。异构硼基络合物结果为 10.32 kcal mol ^-1在单点 CCSD(T) 水平上的能量更高。相比之下，B ₁₁ Au 簇的行为正常，具有拉长的 B ₁₁部分和末端 Au 配体。_{化学键合分析揭示了圆形 B 12} O 簇中的三倍 π/σ 芳香性，包括全局 6π 芳香性，以及空间孤立的内部 2σ 芳香性和外部 10σ 芳香性。三倍的6π/2σ/10σ芳香性是B ₁₂ O簇稳定性的基础。_{对于裸 B 12}星团及其衍生物，这种结合图是未知的。拉长的 B ₁₁ Au 簇具有相互矛盾的 π/σ 芳香性（6π对8σ 电子计数）。B ₁₂O簇实际上与裸B ₁₂簇在离域π/σ键合方面是等电子的，继承了后者的结构和电子鲁棒性。

更新日期：2022-04-25

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